Manufacture of butyl chlorides



April 5, 1932. E1 mAH- D 1,852,063

MANUFACTURE UTYL CHLORIDES Filed Deo. 26. 1922 A Tra R/vsrs Patented Apr. 5, 1932 UNITED' STATES PATENT OFFICE ELOI RICARD, oF NELLE FRANCE, AssrGNon rro socIrlnIcann ALLENrrr a cIE., oF NELLE (DEUX-SVRES), Emmer.

MANUFACTURE F BUTYL CHLOBIDFS Application led December 26, 1922, Serial No. 609,166, and in France December 28, 192.1.

This invention relates to a continuous manufacture of but l chlorides consisting in causing hydrogen c loride to act Without pressure on hot butyl alcohol in presence of a suitable catalyst.

The vessel containing the butyl alcohol and the catalyst is heated to a suitable temperature; a continuous current of hydrogen chloride and butyl alcohol in the desired quantity is run in and there distil continuously the butyl chlorides formed together with the water produced by the reaction. Agitation facilitates the reaction and accelerates it but ijs not indispensable.

The considerable diiference between the boiling points of the chlorides formed and tant and varies with the catalyst and the alcohol used; a part of these oxides distils with the chlorides and the water, the rest remaining in the vessel.

The butyl oxides thus formed'do not diminish the yield orV chlorides because they are themselves esterified by the hydrogen chloride in presence of the same catalysts as easily as are the butyl alcohols. The oxides which have been removed by distillation, therefore, can be returned to the manufacture.

Suitable catalysts are of three sorts 1. Catalysts which have a purely dehydrating action, like sodium sulphate, copper sulphate, magnesium chloride, magnesium sulphate, sulphuric acid, phosphoric acid, s0- dium bisulphate and the like. l

2. Catalysts adapted to form combinations with hydrochloric acid more or less stable,

vor products of addition with hydrochloric acid, such as cuprous chloride, cupric chloride, mercuric chloride, ferrous chloride 4or 45 bismuth chloride.

3. Catalysts which may be regarded as belonging to both the foregoing categories, such as zinc chloride or cadmium chloride.

These catalysts may be used singly or mixed with each other without distinction of catel.gfpry except that they mustvnot be incompatie. a f Whatever catalyst is used, the water which is set free begins to distil as soon as the reaction begins and continues to be eliminated regularly/.without interruption.

The accompanying drawing illustrates diagrammaticallyan arrangement of apparatus suitable for carrying out the present invention. e.

The following examples illustrate'the procedure when apparatus indicated in the accompanying diagram is used.

Eample 1.-'-500 kilos of normal butyl alcohol are charged into a boiler A; 250 kilos .of cupric chloride are added and dissolved by heating, by means of steam or in any other manner, with aid of a double bottom or some other device; there is then introduced into the boiler a `current of hydrogen chloride through the pipe fm..

The acid is absorbed and after a short time butyl chlorides begin to distil. The butyl lchloride vapours traverse a column B by means of which the butyl alcohol carried for- Ward is returned to the boiler A. 4The operation is so controlled that the temperature of the vapours at the top of the'column B is about 80. Butyl alcohol is run regularly from the vessel E through the pipe t to make good the alcohol esteried. The operation can continuein this manner for` several ldays Without sensibly enfeebling the catalyst. The distillate condensed in the condenser C runs into the receiver D where it separates into two layers.

- The upper layer consists almost entirely of butyl chlorides containing a little water,

butyl alcohol and hydrochloric acid. .At the same time thereis present as an impurity a Small quantity of butyl oxide.

his layer is dried and rectified, whereupon it yields normal butyl chloride containing a very small proportion of secondary K butyl chloride.

Y chloric acid through The lower layer consists for the greater part of water containing in solution a little butyl alcohol, hydrochloric acid and butyl chlorides. It is treated with sodium carbonate or in any other manner to recover the butyl alcohol and the chlorides which it contains. A

The yield is approximately that indicated by theory.

It will be understood that, in operating as above described (that is to say, by maintaining a temperatureof 80 C. at the top of column B) the resulting distillate willcontain in the upper layer thereof a binary azeotropic mixture of butyl chloride and water and in the lower layer a binary azeotropic mixture of butyl alcohol and water; and thereby the water is practically all eliminated, makingthe process a continuous one.

Example 2.-The boiler is charged with 500 kilos of isobutyl alcohol and there are added 100 kilos of cadmium oxide. The boiler is heated and the current 'of hydrogen chloride is passed in the manner described in Example l.

Thel apparatus is controlled so as to maintain a temperature of about 70 C. at the top of the column; ony rectification there is-obtained isobutyl chloride.

What I claim is :-V Y

l. The continuous manufactureA of butyl .chloride by the continuous action of hydro.-

chloric acid upon butyl alcohol, which consists in heating the butyl alcohol, in adding a copper chloride thereto, in circulating hydroin distilling the butyl chloride at a temperature where the water will be eliminated as binary azeotropic mixtures respectively with said butyl chloride and the butyl alcohol.

2. The continuous manufacture of butyl A chloride by the continuous action of hydro# chloric acid upon butyl alcohol; which con-- sists in heating the butyl alcohol, in adding a copper chloride thereto, in circulating hydrochloric acid through the butyl alcohol, in distilling thel butyl chloride at a temperature where the water will be eliminated as binary azeotropic mixtures respectively with said butyl chloride and the butyl alcohol, in condensing the distilled product which separates into two layers whereof one contains.

the major part of the butyl chloride and the other the major part of the water, whichis eliminated, and' in the continuous `addition of butyl alcohol and hydrochloric acid to replace the part thereof which was converted into chloride.

. 3. The continuous manufacture of butyl l whereof I have signed this specification.

ELOI RICARD. [La] the butyl alcohol, andiso 

